Article in a sheet form and method for preparation thereof

ABSTRACT

The sheet material produced in accordance with the invention has soft and enriched texture like natural leather and is suitable as any type of artificial leather for shoes, clothes, gloves and the like, particularly for sports gloves.

TECHNICAL FIELD

The present invention relates to a sheet material with extremely lessbleed of softening agent, although the sheet material has naturalleather-tone softness.

BACKGROUND OF THE INVENTION

So as to reproduce the soft and enriched texture of natural leather,artificial leather has been treated traditionally with various agents.However, not any such material close to natural leather has beenobtained yet. For example, a method for softening artificial leather tothe same level as that of natural leather using a certain softeningagent has been known traditionally. In other words, it has been carriedout to bring about texture close to that of natural leather by addingsilicone emulsion processing, wax processing and the like as softeningagents. However, the softness and enriched texture of natural leathercould not be sufficiently brought about successfully. Additionally, thepresent inventors proposed a method for giving an oily material and asupporting material thereof to the surface of a fibrous substrate havingnapped surface, as in accordance with this invention (see PatentReference 1). However, the method intends to improve the touch (oiltone) of the napped surface. Therefore, the method fundamentally is atechnique of attaching a composition including an oily material and asupporting material on the napped part of surface. By the method,accordingly, the overall softness and enriched texture of a fibroussubstrate as in accordance with the invention cannot be obtained. Bythese methods of the related art, in other words, surface touch can beimproved, but soft and enriched texture essential to natural leathercannot be reproduced.

Meanwhile, softening process of artificial leather using stuffingagents, for example fish oil and vegetable oil, for use in naturalleather can produce a material with texture close to that of naturalleather. However, bleed of fats and oils and oils to the surface thereofis distinctly observed. Thus, not any material with great softness andenriched texture close to that of natural leather without any bleed ofoily materials such as fats and oils and oils has been obtained yet.

Patent Reference 1

JP-A-2001-131880

It is an object of the invention to provide a sheet material including afibrous substrate and having great softness and highly enriched textureof natural leather with extremely less bleed of oily materials, as wellas a method for producing the same.

DISCLOSURE OF THE INVENTION

So as to solve the problem, the inventors made investigations, toconsequently find a sheet material and a method for producing the sameas described below.

In other words, the invention relates to a sheet material including theexistence of a blend including an oily material with a viscosity of 50to 10,000 mPa•s at 30° C. and a supporting material thereof, at least inthe inside of a fibrous substrate.

Additionally, the sheet material is a sheet material where the fibercomposing the fibrous substrate is a microfine fiber of 0.3 dtex or lessand where the fibrous substrate includes a fiber-entangled non-wovenfabric and an elastic polymer impregnated in the inside thereof.

The preferable supporting material in accordance with the inventionincludes olefin-series elastomer, aromatic vinyl-series elastomer, anethylene polymer including a unit with a side chain of a hydrocarbongroup with one to 8 carbon atoms at 5 to 60 mol % of the ethylene unitcomposing the main chain or including a block copolymer including ablock of such ethylene polymer, a block copolymer of polymer block Aincluding an aromatic vinyl compound and polymer block B includingconjugated diene, or a hydrogenation product thereof. Additionally,preferable mass ratio of the oily material and the supporting materialin accordance with the invention is 1/1 to 20/1.

Additionally, the invention relates to a suede-type manmade leather or agrain-type manmade leather, where these sheets include the sheetmaterial of the invention, as well as to a sports glove prepared byusing these manmade leather at least partially therein.

The invention also relates to a method for producing a sheet materialincluding preparing a blend including an oily material with a viscosityof 50 to 10,000 mPa•s at 30° C. and a supporting material thereof intoan aqueous dispersion, impregnating a fibrous substrate with the aqueousdispersion and fixing the fibrous substrate.

Preferable modes for carrying out the invention are now described below.However, the invention is never limited by the following descriptions.

First, the supporting material composing the invention is a polymericsubstance exerting elastomer properties at ambient temperature, namelyso-called polymeric substance such that the polymer substance whenprepared into a 0.5-mm thick sheet has extension at 100% or more atambient temperature so the sheet readily deforms when external force isgiven but resumes its original shape when the force is removed. Further,the mass increment of a powder of the polymer substance is 200% or morebecause of its absorption of an oily material used in combinationtherewith, when the powder is impregnated with the oily material, leftto stand alone at ambient temperature for 24 hours and subsequentlyspontaneously filtered. Among them, olefin-series elastomer or aromaticvinyl-series elastomer is preferably used in terms of the retentivity ofthe oily material. First, olefin-series elastomer as a preferableexample of the supporting material of the invention is now described.

The olefin-series elastomer for use in accordance with the invention isa resin including a hydrocarbon chain at the center and has a segmentwith a glass transition point of 0° C. or less. Such example includesfor example EPR (ethylene propylene rubber), EBR (ethylene butylenerubber), HBR (hydrogenated butadiene rubber) and polyisoprene. Themethod for producing these polymers is known. The main raw materialmonomer thereof includes for example olefins such as ethylene,propylene, butene, and octene; and cyclic hydrocarbon compounds anddiene-series hydrocarbon compounds such as isobutylene, cyclopropene,cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, butadiene,isoprene, and norbornene. These monomers are appropriately mixedtogether and polymerized by existing polymerization methods for exampleradical polymerization, an ion polymerization and cation polymerization.So as to increase final physico-chemical properties, particularlyweather durability, hydrogenation is preferably done.

Particularly preferable olefin-series elastomer is a copolymer ofethylene and α-olefin. As the α-olefin, for example, propylene, butene,pentene, hexene, heptene, octene and nonene are included. Thepolymerization method includes for example but is not limited topolymerization, generally in the presence of the Ziegler-Natta catalystor a metallocene catalyst. In this case, an ethylene polymer wherein thecontent of a unit with a side chain of a hydrocarbon group with one to 8carbon atoms is 5 to 60 mol % of the ethylene unit composing the mainchain is preferably used owing to the good elastomer properties and thegreat retentivity of oily material. The molecular weight of sucholefin-series elastomer is a number average molecular weight of severaltens of thousands to several hundreds of thousands, with no specificlimitation. In some case, additionally, a small amount of monomers otherthan α-olefin may satisfactorily be copolymerized therein. Such monomerincludes for example styrene, methyl methacrylate, butyl methacrylateand acrylonitrile.

Aromatic vinyl-series elastomer as one preferable example of thesupporting material composing the invention is now described. Thearomatic vinyl-series elastomer is a block copolymer of polymer block Aincluding an aromatic vinyl-series compound and polymer block B with aglass transition point of 0° C. or less.

The number of the polymer block A in the block copolymer and the numberof the polymer block B therein are not specifically limited. Herein, thepolymer block A is simply referred to as A, while the polymer block B issimply referred to as B. Then, the structure of preferable such blockcopolymer is expressed by structural formulas such as A-B, (A-B)_(n),(A-B)_(n)-A, (B-A)_(n)-B (provided that _(n) represents an integer of 1to 10 in these structural formulas), and (A-B)_(m)X (X representsan_(m)-valent residue of a coupling agent and m represents an integer of2 to 15). Specifically, the triblock copolymer represented by A-B-A isparticularly preferable in terms of the retentivity of oily material.For the retentivity of oily material, the content of an aromatic vinylcompound in the block copolymer is preferably 5 to 75% by mass, morepreferably 10 to 65% by mass.

The aromatic vinyl compound composing the polymer block A in the blockcopolymer includes for example styrene, α-methylstyrene, o-, m- orp-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, andvinylanthracene. Among them, styrene or α-methylstyrene is preferable interms of softness. Such aromatic vinyl compound may be used singly or incombination with two or more thereof.

Additionally, any polymer with a glass transition point of 0° C. or lessis satisfactory as the polymer composing the polymer block B in theblock copolymer, with no specific limitation. In terms of softness,polymers of conjugated diene or hydrogenation products thereof areparticularly preferable. Such conjugated diene includes for example1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and1,3-hexadiene. Among them, preferable are isoprene, 1,3-butadiene ormixtures thereof in terms of softness and preventing the bleed of oilymaterial onto surface. Conjugated diene may be used singly or incombination of two or more thereof.

Among them, generally, resins such as SBS (triblock copolymer includingstyrene polymer block-butadiene polymer block-styrene polymer block),SEBS (triblock copolymer including styrene polymerblock-ethylene•butadiene copolymer block-styrene polymer block), SEPS(triblock copolymer including styrene polymer block-ethylene•propylenecopolymer block-styrene polymer block), SIS (triblock copolymerincluding styrene polymerblock-isoprene polymerblock-styrene polymerblock), and SEEPS (triblock copolymer including styrene polymerblock-ethylene•ethylene•propylene copolymer block-styrene polymer block)can be used as preferable block copolymers in terms of the retentivityof such oily material and the texture of the resulting fiber substrate.

With no specific limitation, the number average molecular weight of theblock copolymer is preferably 50,000 to 500,000, more preferably 100,000to 400,000. When the number average molecular weight is less than50,000, the retentivity of such oily material is deteriorated. Above500,000, the softness is deteriorated.

Such block copolymers have already been known. As the method forproducing such copolymers, for example, the following known anionpolymerization method can be used. Specifically, an aromatic vinylcompound and conjugated diene are polymerized together in an inertorganic solvent such as n-hexane and cyclohexane, using for example analkyl lithium compound as an initiator, to prepare such block copolymer.If desired, then, coupling agents such as dichloromethane, carbontetrachloride and tetrachlorosilane may be used.

In case that the block copolymer is to be a hydrogenation product ofsuch a block copolymer as described above, such block copolymer ishydrogenated in the presence of a hydrogenation catalyst in an inertorganic solvent by known methods, to obtain a hydrogenated blockcopolymer.

In accordance with the invention, further, the block copolymer or ahydrogenated block copolymer as the hydrogenation product thereof isused as the supporting material. From the standpoints of thermalresistance and weather durability, the hydrogenated block copolymer ismore preferable, where 70% or more of the carbon-carbon double bondsderived from conjugated diene in the block copolymer beforehydrogenation is still more preferably hydrogenated. The content of thecarbon-carbon double bonds in the polymer block B in the hydrogenatedblock copolymer can be determined by iodine value determination,infrared spectrophotometer, nuclear magnetic resonance and the like. Inaddition to the two types of the blocks, other monomers maysatisfactorily be copolymerized in a block form or randomly, within arange with no deterioration of the invention. Further, thestyrene-series elastomer may satisfactorily include styrene-containingrubber such as SBR (styrene butadiene rubber) other than the blockcopolymer described above.

Concerning the resin composing the supporting material for use inaccordance with the invention, additionally, the resin may containfunctional groups such as carboxyl group, hydroxyl group, acid anhydridegroup, amino group and epoxy group within the molecular chain or atmolecular ends thereof, unless the scope of the invention isdeteriorated.

The oily material to be blended in such supporting material shouldessentially be a fluid material with a viscosity of 50 to 10,000 mPa•sat 30° C. and with no miscibility with water at ambient temperature sothat the oily material is separated from water into a phase. In casethat the viscosity is less than 50 mPa•s, the oily material aftercoating on the substrate starts to bleed. In case that the viscosityexceeds 10,000 mPa•s, the oily material is never miscible with thesupporting material, so that the resulting sheet material has poor oiltone and lacks softness. Thus, such oily material is not suitable.

Specific examples of the oily material type include paraffin-series ornaphthene-series process oil, white oil, mineral oil, oligomer ofethylene with α-olefin, paraffin wax, fluid paraffin, silicone oil,vegetable oil and aromatic oil. These may be used singly or in mixture.Among them, paraffin-series process oil is preferable because theprocess oil has an oil tone similar to that of natural leather.

In accordance with the invention, preferably, the mass ratio between thesupporting material (1) and the oily material (2) is (2)/(1)=1 to 20.When the mass ratio is less than 1, soft texture is hardly broughtabout. When the mass ratio exceeds 20, the bleed of the oily materialreadily occurs. More preferably, the mass ratio is within a range of(2)/(1)=3 to 12.

In accordance with the invention, the type and molecular weight of thesupporting material (1), the type of the oily material (2), the massratio of two or more oily materials when used in mixture, the ratio(2)/(1), and the amounts thereof to be given to the inside of thefibrous substrate can be modified to reproduce the desired softness andenriched texture of natural leather.

The method for giving them to the inside of the fibrous substrateincludes for example a step of dissolving a blend including an oilymaterial with a viscosity of 50 to 10,000 mPa•s at 30° C. and asupporting material thereof in a good solvent to prepare a solution, astep of impregnating the fibrous substrate with the solution, a step ofremoving the solvent and a step of fixing the fibrous substrate.However, a method including a step of preparing a blend including anoily material with a viscosity of 50 to 10,000 mPa•s at 30° C. and asupporting material thereof into an aqueous dispersion, a step ofimpregnating the fibrous substrate with the aqueous dispersion, and astep of drying and fixing the fibrous substrate should be selected froman environmental standpoint and a quality standpoint such that greatsoftness and enriched texture like those of natural leather can befinally yielded with scarce formation of continuous film duringimpregnation.

The order to give them to the inside of the fibrous substrate is notspecifically limited. As long as the supporting material and the oilymaterial are contained in the inside of the final product, theadvantages of the invention can be exerted. In case of intending thepreparation of suede-type artificial leather including microfine fiberand being fully covered with nap, however, the above process ispreferably done after dyeing because the oily component is then lessdissociated during dyeing so that the process can be controlled veryeasily.

The fibrous substrate for use in accordance with the invention is nowdescribed. As such, known fibrous substrates can be used, with nospecific limitation. Known fibrous substrates can be used, including forexample woven fabric, non-woven fabric, knitted fabric or productsprepared by impregnating these fabrics with polymeric elastomers,entangled non-woven fabric or products prepared by impregnating thefabric with polymeric elastomers, microfine fiber-entangled non-wovenfabric, or products prepared by impregnating the fabric with polymericelastomers.

A fibrous substrate prepared by impregnating a non-woven fabricentangled with a microfine fiber composed of a fiber of 0.3 dtex or lesswith a polymeric elastomer is preferably used because the resultingsheet material can get softness like natural leather. A range of 0.1 to0.0001 dtex is more preferable. When the fiber is thick above 0.3 dtex,the texture of the napped surface of the resulting intended suede-typemanmade leather is rough, leading to the deterioration of theappearance. When the thickness of the fiber is less than 0.0001 dtex,the break strength of the fiber is decreased, so that the peel strengthand break strength of the resulting layer are decreased andadditionally, no sufficient coloring is likely to be obtained.

The method for producing such microfine fiber typically includes forexample a method including a step of producing microfine fiber-formingfibers by methods such as a method for producing a fiber of sea-islandstructure by for example a mix spinning method and a composite spinningmethod of sea-island type, using two or more polymers with immiscibilitywith each other at their molten states and with difference in solubilityor decomposition, and a method for producing a division type compositefiber by a composite spinning method, and a subsequent step ofextracting and removing or decomposing and removing a part thereof (forexample, the sea component) to prepare a microfine fiber; or a methodincluding a step of releasing polymers in a division type compositefiber from each other at the interface thereof to prepare a microfinefiber. Other than these methods described above, methods such asso-called melt-blow method including injecting a fiber-forming polymerfrom a melt spinning nozzle and immediately blowing the polymer off witha high-speed gas to make the resulting fiber thin may also be used. Dueto the control of fiber thickness and the stability of the resultingmicrofine fiber, however, the method en route the microfinefiber-forming fiber is preferable.

The resin composing the microfine fiber in accordance with the inventionincludes for example but is not limited to aromatic polyesters such aspolyethylene terephthalate, polypropylene terephthalate, polybutyleneterephthalate, polyethylene naphthalate, and copolymer polyesters mainlyincluding them; polyamides such as nylon-6, nylon-66, and nylon-610; andpolyolefins such as polyethylene and polypropylene. Among them, thearomatic polyesters and polyamides described above are preferablebecause artificial leather with natural leather tone can be producedfrom them and the dyeability thereof is great. To these resins maysatisfactorily be added pigments typically including carbon black,coloring agents such as dyes and known stabilizers typically includingultraviolet preventive agents, within a range without any deteriorationof the stability during spinning.

Additionally, examples of the resin component composing the microfinefiber-forming fiber, which are to be extracted and removed or decomposedand removed, include at least one polymer selected from polymers such aspolyethylene, polypropylene, ethylene-propylene copolymer,ethylene-vinyl acetate copolymer, polystyrene, styrene-acrylic monomercopolymer, styrene-ethylene copolymer and copolymer polyester. Amongthem, polyethylene, polystyrene or copolymers mainly including them arepreferable due to ready extraction.

As a method for forming a fibrous substrate including an entanglednon-woven fabric including the microfine fiber or microfinefiber-forming fiber and an elastic polymer impregnated in the insidethereof, known methods are used. For example, the method can besuccessfully attained by sequentially carrying out a step of producingan entangled non-woven fabric including the microfine fiber-formingfiber, a step of impregnating the entangled non-woven fabric with anelastic polymer solution for solidification, and a step of modifying themicrofine fiber-forming fiber into a microfine fiber. It is needless tosay that the step of modification into microfine fiber and the step ofimpregnation with the elastic polymer solution for solidification may becarried out in an inversed order.

The method for producing such entangled non-woven fabric using themicrofine fiber-forming fiber includes a method of treating themicrofine fiber-forming fiber by spinning, drawing, thermal fixation,crimping, and cutting by methods having been known traditionally, toprepare a staple of the fiber, splitting such staple with a curd to forma random web or cross-lap web with a weber, and laminating the resultingweb together if necessary to adjust the web to a desired weight. Then,the weight of the web is appropriately selected, depending on the fieldof a final intended use. Generally, the weight is preferably within arange of 100 to 3,000 g/m². For the purpose of the preparation at lowcost, efficiently, two sheets of a fibrous substrate can be produced atonce efficiently by impregnating a entangled non-woven fabric of amassabout 2-fold the required mass with an elastic polymer solution forsolidification and dividing the resulting non-woven fabric by halvesalong the thickness direction with a band knife.

Subsequently to the lamination of the web, the laminate is treated at anentangling process by known methods for example needle punching methodor high-pressure water jet method to form an entangled non-woven fabric.Generally, conditions in case of needle punching method are preferablyset within a range of 200 to 2,500 punch/cm², although the range variesdepending on the shape of used needle and the thickness of the web.

Prior to the impregnation treatment with an elastic polymer, theentangled non-woven fabric is treated by known methods such as thermalpress if necessary for smoothing the surface. In case that the fibercomposing the entangled non-woven fabric is a fiber of a sea-islandstructure including polyethylene as the sea component and polyester orpolyamide as the island component, polyethylene as the sea component isfused together by thermal press, to fix the fiber together via adhesionto prepare an entangled non-woven fabric with great surface smoothness.In case that the fiber composing the entangled non-woven fabric is notin a sea-island structure which can be modified into a microfine fiberby dissolving and removing one component therein, preferably, the fibersurface is covered with a temporary filler such as polyvinyl alcoholprior to the impregnation treatment with an elastic polymer, from whichthe temporary filler is removed after the elastic polymer is given, soas to prevent the fixation of the elastic polymer used for impregnationto make the texture hard. In case that the fiber composing the entanglednon-woven fabric is in a sea-island structure which can be modified intoa microfine fiber by dissolving and removing one component therein, thetemporary filler is given at the stage of the entangled non-woven fabricto cover the surface of the multi-component fiber, and the temporaryfiller is then removed after the elastic polymer is given, to prepare asofter sheet.

As the resin for impregnation of the entangled non-woven fabric, knownelastic polymers can be used, including for example natural rubber,styrene-butadiene copolymer, acrylonitrile-butadiene copolymer,polyurethane elastomer, other synthetic rubber or mixtures thereof.Among them, polyurethane resin is preferably used in view of greattexture. Preferable polyurethane resin includes so-called segmentedpolyurethane obtained by using at least one polymer diol with a numberaverage molecular weight of 500 to 5,000 as soft segment, which isselected from the group consisting of polyester-series diol,polyacetone-series diol, polycarbonate-series diol, polyether-seriesdiol and polyether ester-series diol as obtained by reacting diol withdicarboxylic acid or a derivative thereof with an ability to form ester,and then reacting this polymer diol with a diisocyanate compound and anextension agent of low-molecular chain.

The diol compound for use in the synthesis of the polymer diol composingthe soft segment is preferably aliphatic compounds with 6 or more carbonatoms to 10 or less carbon atoms in terms of durability or leather-liketexture and includes for example 3-methyl-1,5-pentane diol, 1,6-hexanediol, 2-methyl-1,8-octane diol, 1,9-nonane diol, and 1,10-decane diol.Further, typical examples of the dicarboxylic acid include for examplealiphatic dicarboxylic acids such as succinic acid, glutaric acid,adipic acid, azelaic acid, and sebacic acid; and aromatic dicarboxylicacids such as terephthalic acid and isophthalic acid.

In case that the number average molecular weight of polymer diol is lessthan 500, unpreferably, the resulting sheet material lacks softness sothat no natural leather-like texture can be obtained. In case that thenumber average molecular weight of polymer diol exceeds 5000, further, amanmade leather balanced in softness, durability, thermal resistance andhydrolysis resistance can hardly be obtained because the concentrationof urethane group is decreased therein. The diisocyanate compoundincludes aromatic, aliphatic and alicyclic diisocyanate compounds suchas 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, tolylenediisocyanate, isophorone diisocyanate,dicyclohexylmethane-4,4′-diisocyanate, and hexamethylene diisocyanate.

Additionally, the extension agent of low-molecular chain includes forexample low-molecular compounds with a molecular weight of 300 or lessand with two active hydrogen atoms, such as ethylene glycol, propyleneglycol, butane diol, hexane diol, N-methyldiethanolamine,ethylenediamine, diaminodiphenylmethane, diaminodicyclohexylmethane, andisophorone diamine.

The method for synthetically preparing polyurethane may include one-shotmethod or prepolymer method.

If necessary, further, solidification adjusters, stabilizers and thelike may satisfactorily be added to polyurethane, within a range withoutany deterioration of the object of the invention. Further, otherpolymers may be used in combination. Additionally, coloring agents suchas carbon black and dyes may be added.

The method for allowing the entangled non-woven fabric to containpolyurethane, from the standpoint of obtaining balanced texture,includes for example but is not limited to a method including directlyimpregnating the entangled non-woven fabric with a polyurethane solutionprepared by diluting polyurethane with a good solvent for polyurethane,typically including dimethylformamide or with an aqueous polyurethanedispersion and squeezing the resulting fabric with a mangle, ifnecessary, a method including coating the fabric with a polyurethanesolution or an aqueous polyurethane dispersion by coaters to infiltratethe solution or the dispersion into the fabric. By wet solidification ordry solidification of the impregnated polyurethane solution,polyurethane is contained in the entangled non-woven fabric. From thestandpoint of obtaining natural leather-like texture and touch, inparticular, wet solidification is preferable. From the standpoint ofnatural leather-like soft texture, additionally, the mass ratio betweenthe fiber composing the fibrous substrate and polyurethane is preferablywithin a range of 30/70 to 90/10, more preferably within a range of35/65 to 80/20. When the fiber ratio is too small compared with therange, the resulting manmade leather has rubber-like texture. When thefiber ratio is too high, the resulting sheet has such paper-liketexture. Therefore, the intended natural leather-like texture cannot beobtained.

In case of using a fiber of sea-island structure, the entanglednon-woven fabric is impregnated with polyurethane and subsequentlytreated with a liquid functioning as a solvent-free for polyurethane andthe island component of the microfine fiber-forming fiber andfunctioning as a solvent or decomposition agent for the sea component ofthe microfine fiber-forming fiber, to modify the microfine fiber-formingfiber into a microfine fiber bundle, to prepare a fibrous substrateincluding the microfine fiber-entangled non-woven fabric andpolyurethane. It is needless to say that a method for modifying themicrofine fiber-forming fiber into a microfine fiber bundle prior toimpregnation with polyurethane may also be used to prepare a fibroussubstrate. In case of using a releasable composite fiber of divisiontype, further, a method may be possible including treating the fiberwith a liquid promoting the release, to release the fiber at theinterface of the fiber-composing polymers to prepare a microfine fiberbundle.

Then, the resulting fibrous substrate can be finally prepared intomanmade leathers with the surface processed by known finish techniques,such as suede-type manmade leather with at least one face being nappedor grain-type manmade leather with the surface prepared with a polymericelastomer. The fibrous substrate including the resulting microfinefiber-entangled non-woven fabric and polyurethane is napped by knownmethods typically including buffing with sand paper and needle cloth,and smoothing nap. Because the nap length raised has influences on theappearance and the appearance thereof after coating with a supportingmaterial containing an oily material, the nap length is adjusted byselecting conditions for buffing and nap smoothing, for example the sandpaper No. for use in buffing, the grind speed and the pressure at whichthe substrate is pressed. Nap may satisfactorily exist on the wholesurface of a single face of the resulting sheet or on the whole surfaceof both the faces thereof, or may exist in a spot form on a part of asingle face or both the faces thereof.

Known dyeing methods for dyeing knitted woven fabric or non-woven fabriccan be used as the dyeing method, with no specific limitation.Additionally, known dyes may satisfactorily be used as the dye for use.In one example, satisfactorily, dispersion dyes are used in case thatthe resin on the napped part of the fibrous substrate is polyester,while acid dyes; sulfur dyes and vat dyes are used in case that theresin thereon is polyamide; and cation dyes are used in case that theresin thereon is acryl. Further, any known dyeing machines can be usedwith no specific limitation, including for example circular, wince, dashline, washer dyeing machine, Tyco dyeing machine and continuous dyeingmachine.

A blend including the oily material and a supporting material thereof isgiven to the inside of the fibrous substrate thus obtained. The methodfor giving the blend includes for example impregnation-liquid squeezingmethod with mangle, coating method, and spray method. Among them, theimpregnation-liquid squeezing method with mangle is preferably used. Theobject of the invention can first be achieved by the presence of theblend including the oily material and the supporting material in theinside of the fibrous substrate. In case that the oily material and thesupporting material exists only on the surface but is absent in theinside, the natural leather-tone softness and superior enriched textureas intended in accordance with the invention cannot be attained.

The ratio between the fibrous substrate in accordance with the inventionand the blend including the oily material and the supporting materialthereof is preferably within a range of 5 to 80%, more preferably withina range of 10 to 50% of the fibrous substrate, in view of naturalleather-tone softness and texture. When the ratio is less than 5%, oiltone is so poor that the resulting sheet is likely to have hard texture.When the ratio exceeds 80%, the sticky touch of oil is likely to beenhanced.

In case that the sheet material of the invention is used to prepare asuede-type manmade leather, the presence of the blend in a mannerlimited to the inside of the sheet can bring about soft sheet withoutany modification of the surface suede texture.

The suede-type manmade leather thus obtained is useful as a material notonly for shoes but also as materials for gloves, bags, and clothes andsometimes as a material for sports gloves.

EXAMPLES

The invention is now described specifically in Examples, but theinvention is not limited by these Examples. The term “part” in theExamples relates to mass unless otherwise stated.

The thickness of fiber was determined using an photomicrograph of thecross section of the fiber and on the basis of the mean of thecross-sectional area thereof.

In the Examples, softness and enriched touch were determined by theinventors, when they grasped manmade leather with hands at variousintensities or when they wore sports gloves prepared using manmadeleather on hands and then opened or closed their hands to feel generaltexture of the sports gloves. The results of their assessment wereexpressed as follows.

Great: circle

Good: triangle

Poor: x.

Further, oil bleed (bleed) was assessed by the following method,including by determining whether or not oily matters were deposited onhands when manmade leather was strongly held with clean washed hands,whether or not oily matters were deposited on hands when sports glovesprepared using manmade leather were worn on clean washed hands and thehands were then strongly closed or opened, or the extent of thedeposition. The results of their assessment were expressed as follows.

Great: circle

Good: triangle

Poor: x.

Example 1

Nylon-6 and polyethylene were mixed together at their chip states at amass ratio of 50:50 for melt spinning with an extruder, to spin a fiberof a sea-island structure where polyethylene was the sea component andnylon-6 was the island component; by drawing, crimping and cutting, astaple of 4 dtex and 51-mm length was prepared to prepare a cross-lapwith a webber, which was then treated by needle punching at 700punch/cm², using a needle punching machine to finally obtain anentangled non-woven fabric. The non-woven fabric was impregnated with adimethylformamide (sometimes abbreviated as DMF hereinafter) solution ofa polyurethane resin including poly (3-methylpentane) adipate diol andpolyethylene glycol as polymer diols of a mean molecular weight of 2000for soft segment, followed by wet solidification, from whichpolyethylene as the sea component of the fiber was extracted intoperchloroethylene, to prepare a fibrous substrate with a weight of 450g/m², a thickness of 1.3 mm and a polyurethane to fiber ratio of 40/60.The fineness level of the nylon microfine fiber in the resultingsubstrate was 0.006 dtex on average. The single face of the resultingsubstrate was buffed with a sand paper, to prepare a sheet materialincluding the nylon microfine fiber and having a napped surface. Thesheet material was dyed under the following conditions with a circulardyeing machine, to obtain suede-type manmade leather in brown.

Dyeing conditions

Dye:

Lanacron Brown S-GR (manufactured by Ciba Specialty Chemicals K.K.); 5%owf

Irgalan Yellow GRL (manufactured by Ciba Specialty Chemicals K.K.); 2%owf

Bath ratio: 1:30

Dyeing temperature: 90° C.

Using then a hydrogenated styrene-(ethylene•ethylene•propylene)-styrenetriblock copolymer of a number average molecular weight of about 290,000(“Septon 4055” elastomer manufactured by Kuraray Co., Ltd.;hydrogenation ratio of 98%; after the copolymer was left to stand in thefollowing oily material at ambient temperature for 24 hours, the massincrement was 1600%) as a supporting material, a paraffin-series oil atan 8-fold mass ratio as an oily material (“PW-90” manufactured byIdemitsu Kosan Co., Ltd.; viscosity at 30° C.: 140 mPa•s) was blended inthe supporting material, to prepare an aqueous dispersion (mean particlediameter of 1 μm) at a concentration of the non-volatile components at30%.

Using a mangle, the aqueous dispersion was impregnated into thesuede-type manmade leather dyed in brown to a liquid squeezing ratio of70%, which was then dried in a dryer at 60° C. to prepare a suede-typemanmade leather at a mass ratio of the blend including the oily materialand the supporting material thereof to the fibrous substrate being 20%.The resulting suede-type manmade leather had great natural leather-tonesoftness and enriched texture. Additionally, no oil bleed existed.

Using the resulting suede-type manmade leather, sports gloves wereprepared. The sports gloves had soft texture without any oil bleed ontothe surface and were greatly fitted for hands.

Further, the gloves were washed under the conditions according to themethod A-1 described in JIS L0884 and dried at 70° C., for wear test.Because of almost no dissociation of the blend given, the soft texturewas retained while the gloves were greatly fitted for hands.

Example 2

The aqueous dispersion prepared in Example 1 was impregnated into thesuede-type manmade leather dyed in brown as prepared in Example 1 with amangle, to a liquid squeezing ratio of 60%, which was then dried in adryer at 90° C. to prepare a suede-type manmade leather at a mass ratioof the blend including the oily material and the supporting materialthereof to the fibrous substrate being 18%. The resulting suede-typemanmade leather had great natural leather-tone softness and enrichedtexture. Additionally, no oil bleed existed.

Using the resulting suede-type manmade leather, sports gloves wereprepared. The sports gloves had soft texture without any oil bleed ontothe surface and were greatly fitted for hands.

Further, the gloves were washed under the conditions according to themethod A-1 described in JIS L0884 and dried at 70° C., for wear test.Because of almost no dissociation of the blend given, soft texture wasretained while the gloves were greatly fitted for hands.

Example 3

The fibrous substrate obtained in Example 1 was sliced along thedirection of the thickness thereof with a slicer into two sheets.Further, the sliced face was ground with a buff machine, to prepare afibrous substrate of a thickness of 0.5 mm. The fibrous substrate wasdyed into black under the following conditions with a circular dyeingmachine and then dried, to prepare a fibrous substrate in gray. Dyeingconditions Dye:Kayakalan Black 2RL (manufactured by Nippon Kayaku Co.,Ltd.) Dye concentration: 2% OWF Leveling agent: 2 g/l Dyeingtemperature: 90° C. Dyeing period: 60 minutes

The fibrous substrate in gray was dry treated of the surface under thefollowing conditions. Surface-treating conditions Release paper:DE-123(Dai Nippon Printing Co., Ltd.) Composition of top layer NY-324(manufactured by Dainippon Ink 100 parts and Chemicals Incorporation)L-1770S (Dilac color; manufactured by 20 parts Dainippon Ink andChemicals, Inc.) DMF 35 parts Composition of adhesive agent LeathermineUD 8310 (manufactured by Dainichiseika 100 parts Color and ChemicalsMfg. Co., Ltd.) Takenate D-110 N (manufactured by Takeda 10 partsPharmaceutical Company Limited) Accelerator Accel QS (manufactured by 2parts Dainippon InkAnd Chemicals, Inc.) Ethyl acetate 20 parts

The cross section of the resulting grain-type manmade leather wasphotographed with a scanning electron microscope, to measure thethickness of the resin layer on the surface-treated (grain) part. Thetop layer was 15 Mm, while the adhesive layer was 35 μm. The aqueousdispersion used in Example 1 was impregnated into the grain-type manmadeleather with a mangle to a liquid squeezing ratio of 60%, which was thendried in a dryer at 90° C. to prepare a grain-type manmade leather at amass ratio of the blend including the oily material and the supportingmaterial thereof to the fibrous substrate being 18%. The resultinggrain-type manmade leather was then crimped with a tumbler dryer, toprepare a grain-type manmade leather in black. The resulting grain-typemanmade leather had great natural leather-like softness and enrichedtexture. Additionally, no oil bleed existed. Further, the grain-typemanmade leather was most suitable for clothes, gloves and bags.

Using the resulting grain-type manmade leather, sports gloves wereprepared. The sports gloves had soft texture without any oil bleed ontothe surface and were greatly fitted for hands.

Further, the gloves were washed under the conditions according to themethod A-1 described in JIS L0884 and dried at 70° C., for wear test.Because of almost no dissociation of the blend given, soft texture wasretained while the gloves were greatly fitted for hands.

Example 4

For preparing a fibrous substrate by the same method as in Example 1,the mass of the non-woven fabric after needling was adjusted to 700g/m². Subsequent impregnation with polyurethane, solidification andextraction were done by the same methods as in Example 1, to obtain asubstrate of a weight of 705 g/m² and a thickness of 2.1 mm. The surfaceof the fibrous substrate was coated under the following conditions andwas subsequently charged in aqueous 5% DMF solution to solidifypolyurethane, to prepare a black foam layer (thickness of 500 μm) on oneface of the fibrous substrate. Coating conditions Composition of foamlayer Crisbon MP-105 (manufactured by Dainippon 100 parts Ink andChemicals, Inc.) DILAC L6001 (manufactured by Dainippon Ink 10 parts andChemical, Inc.) Crisbon Assister SD-7 (manufactured by 2 parts DainipponInk and Chemicals, Inc.) Crisbon Assister SD-11 (manufactured by 1 partDainippon Ink and Chemicals, Inc.) Crisbon Assister SD-17 (manufacturedby 2 parts Dainippon Ink and Chemicals, Inc.) DMF 60 parts Coatingamount 300 g/m²

The foam layer was embossed in a calf-like tone with an emboss machine,to prepare a grain-type manmade leather. The aqueous dispersion preparedin Example 1 was used for impregnation of the grain-type manmade leatherwith a mangle, to a liquid squeezing ratio of 60%, which was then driedin a dryer at 90° C., so that the mass ratio of the blend including theoily material and the supporting material thereof to the fibroussubstrate was 18%. Subsequently, the sheet was crimped with a tumblerdryer to prepare a black grain-type manmade leather with great naturalleather-tone enriched and soft texture. The resulting grain-type manmadeleather was the most suitable for gloves, shoes and the like.

Example 5

The supporting material and the oily material in Example 1 were changedto EPR (EP 961 SP: elastomer manufactured by JSR: after the elastomerwas left in the following oily material at ambient temperature for 24hours, the mass increment was 1500% and the content of hydrocarbongroups in the side chain was 20 mol %) as a supporting material and aparaffin-series oil at a 2-fold mass ratio as an oily material (PW-380:manufactured by Idemitsu Kosan Co., Ltd.; the viscosity at 30° C. was600 mPa•s). These were blended together to prepare an aqueous dispersionat a concentration of the non-volatile components being 30%. By the samemethod as in Example 1 except for the use of the aqueous dispersion inplace of the blend in Example 1, suede-type manmade leather wasprepared. The mass ratio of the blend including the oily material andthe supporting material thereof to the fibrous substrate composing theresulting suede-type manmade leather was 20%. The resulting suede-typemanmade leather had great natural leather-like softness and enrichedtexture. Additionally, no oil bleed existed.

Using the resulting suede-type manmade leather, sports gloves wereprepared. The sports gloves had soft texture without any oil bleed ontothe surface and were greatly fitted for hands.

Further, the gloves were washed under the conditions according to themethod A-1 described in JIS L0884 and dried at 70° C., for wear test.Because of almost no dissociation of the blend given, soft texture wasretained while the gloves were greatly fitted for hands.

Comparative Example 1

In the same manner as in Example 1 except for no use of the blend ofExample 1, a suede-type manmade leather was obtained. The resultingsuede-type manmade leather was like rubber without any oil tone and hadpoorly enriched texture. The texture was greatly inferior compared withthe suede-type manmade leather of Example 1. Using the resultingsuede-type manmade leather, sports gloves were prepared. The sportsgloves had poorer enriched touch and harder texture and were more poorlyfitted for hands, compared with the sports gloves obtained in Example 1.

Comparative Example 2

In the same manner as in Example 1 except for the use of an aqueoussolution of a silicone-series softening agent (“Nicca silicone AM-204”at a solid concentration of 20% as manufactured by Nicca Chemical Co.,Ltd.) for the fibrous substrate in place of the blend of Example 1, asuede-type manmade leather was obtained. The resulting suede-typemanmade leather lacked the enriched touch unique to oil and had atexture absolutely different from the natural leather-tone texture,although the sheet had softness.

Using the resulting suede-type manmade leather, sports gloves wereprepared. The sports gloves had poorer enriched touch, compared with thesports gloves obtained in Example 1.

Further, the gloves were washed under the conditions according to themethod A-1 described in JIS L0884 and dried at 70° C., for wear test.The silicone-series softening agent given was almost totallydissociated. The texture of the gloves changed to hard texture, and thegloves were poorly fitted for hands.

Comparative Example 3

Using the suede-type manmade leather dyed in brown at a state with noimpregnation with any blend, as produced in Example 1, the sheet wasimpregnated with the stuffing agent (sulfonated natural oil) for use innatural leather and was then dried, to the impregnation of a stuffingagent at a mass ratio of the stuffing agent to the fibrous substratecomposing the suede-type manmade leather being 16%. The texture of theresulting suede-type manmade leather had great enriched texture andsoftness. However, the stuffing agent was deposited much on hands orpaper, when the suede-type resulting manmade leather was held with thehands and additionally when the sheet was simply laid on the paper.Thus, the bleed of the stuffing agent was distinct. Using the resultingsuede-type manmade leather, sports gloves were prepared. The sportsgloves had softness and enriched texture, comparable to those of thesports gloves obtained in Example 1. After the gloves were taken offhowever, very unpleasant sticky touch remained on hands.

Further, the gloves were washed under the conditions according to themethod A-1 described in JIS L0884 and dried at 70° C., for wear test.The stuffing agent given was almost totally dissociated. The texture ofthe gloves changed to hard texture, and the gloves were poorly fittedfor hands.

Comparative Example 4

The same oily material and supporting material as in Example 1 wereblended together at the same ratio as in Example 1. Subsequently, theresulting blend was not prepared into an aqueous dispersion but wasdissolved in toluene to prepare a toluene solution (at 20% of thenon-volatile components).

In the same manner as in Example 1 except for no use of the blend inExample 1, a suede-type manmade leather in brown was obtained. Thetoluene solution (at 20% of the non-volatile components) was coated onthe napped surface of the resulting brown suede-type manmade leather toa solid deposition of about 7 g/m² with a gravure roll of 55 mesh, andwas then dried to evaporate toluene. The blend was deposited only on thenapped surface of the resulting suede-type manmade leather. No oil bleedexisted. However, the texture lacked both softness and enriched touch,and was not significantly different from that of the suede-type manmadeleather after dyeing. Using the resulting suede-type manmade leather,sports gloves were prepared. Compared with the sports gloves obtained inExample 1, the sports gloves had poorer softness and no enriched textureand were poorly fitted as well.

Further, the gloves were washed under the conditions according to themethod A-1 described in JIS L0884 and dried at 70° C., for wear test.The dissociation of the blend deposited only on the napped surface wasnot observed, but the hard texture prior to washing never changed. Thegloves were poorly fitted for hands.

The properties of the manmade leathers obtained in the above Examplesand Comparative Examples are shown in Table 1.

INDUSTRIAL APPLICABILITY

The sheet material of the invention has both enriched and soft texturessimilar to those of natural leather and has good durability againstwashing. Suede-type manmade leather and grain-type manmade leatherprepared from the sheet material of the invention are suitable for anyapplications such as shoes, clothes, gloves or bags or interiorarticles. Such sheet is particularly useful for the application tosports gloves owing to the great softness, enriched touch andfittingness. TABLE 1 Item Softness Enriched touch Oil bleed Example-1 ∘∘ ∘ Example-2 ∘ ∘ ∘ Example-3 ∘ ∘ ∘ Example-4 ∘ ∘ ∘ Example-5 ∘ ∘ ∘Comparative Example-1 x x ∘ Comparative Example-2 ∘ x ∘ ComparativeExample-3 ∘ ∘ x Comparative Example-4 x x ∘

1. A sheet material comprising an oily material with a viscosity of 50to 10,000 mPa•s at 30° C. and a supporting material thereof, at least inthe inside of a fibrous substrate.
 2. The sheet material according toclaim 1, wherein said fibrous substrate comprises a microfine fiber of0.3 dtex or less.
 3. The sheet material according to claim 1, whereinthe fibrous substrate comprises a fiber-entangled non-woven fabric andan elastic polymer impregnated into the inside thereof.
 4. The sheetmaterial according to claim 1, wherein said supporting material is anolefin-series elastomer.
 5. sheet material according to claim 1, whereinsaid supporting material is an aromatic vinyl-series elastomer.
 6. Thesheet material according to claim 1, wherein said supporting material isan ethylene polymer comprising a unit with a side chain of hydrocarbongroups with one to 8 carbon atoms at 5 to 60 mol % of the ethylene unitcomprising the main chain or comprising a block copolymer comprising ablock of ethylene polymer.
 7. The sheet material according to claim 1,wherein said supporting material is a block copolymer comprising polymerblock A which comprises an aromatic vinyl compound and polymer block Bwhich comprises conjugated diene, or is a hydrogenation product thereof.8. The sheet material according to claim 1, wherein the mass ratiobetween said oily material and said supporting material is 1/1 to 20/1.9. A suede-type manmade leather comprising said sheet material accordingto claim
 1. 10. A grain-type manmade leather comprising said sheetmaterial according to claim
 1. 11. A sports glove comprising saidmanmade leather according to claim
 9. 12. A method for producing a sheetmaterial, said method comprising preparing a blend comprising an oilymaterial with a viscosity of 50 to 10,000 mPa•s at 30° C. and asupporting material thereof into an aqueous dispersion, impregnatingsaid aqueous dispersion into the inside of a fibrous substrate andfixing said fibrous substrate.
 13. A sports glove comprising saidmanmade leather according to claim 10.